Certain substituted bis-anthraquinonyl bibenzothiazole and bibenzoxazole dyes and process



United States Patent CERTAIN. SUBSTITUTED BIS-ANTHRAQUINONYL BIBENZOTHIAZOLE AND BIBENZOXAZOLE DYES AND PROCESS Riitger Neelf, Leverkusen-Bayerwerk, Germany, assignor to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany No Drawing. Application September 5, 1956 Serial No. 607,998

Claims priority, application Germany September 7, 1955 5 Claims. (Cl. 260-303) This invention relates to vat dyestuflis and to a process for producing the same.

It is an object of the present invention to provide novel vat dyestuffs. A further object is to provide vat dyestuffs which exhibit good fastness properties and especially a great strength of color. Further objects will appear hereinafter.

It has been found that new vat dyestuffs of the thiazole and oxazole series are obtainable by converting l-aminoanthraquinone-Z-aldehydes or their aniles substituted in the anthraquinone nucleus with o-amino-phenols or oamino-thiophenols into the corresponding o-hydroxyor o-mercapto-azomethines, and subsequently subjecting them to a dehydro-cyclization with oxidizing compounds, if desired, in the presence of alkaline agents, or by converting the 1-amino-anthraquinone-Z-aldehydes or their aniles with aromatic amines into the corresponding azomethines and by treating these with sulfur, if desired, in the presence of a diluent such as naphthalene at elevated temperatures.

Substituted anthraquinones which are suitable for the process of the present invention are, for example, the 6-chloro-, 7-chloro-, 6,7-dichloroand 6(7)-chloro-1- amino-anthraquinone-Z-aldehydes or the 4-acylaminoor S-acylamino derivatives of the 4- or S-amino derivatives which may subsequently be acylated.

Examples of suitable o-amino-phenols or o-amino-thiophenolsare pand o-toluidine, benzidine, naphthylamine, p-phenylene-diamine, l-hydroxyor l-mercapto-naphthylamine, o-aminophenol, o-aminothiophenol, o,o-dihydroxyand o,o'-dimercapto-benzidine or o-hydroxyor o-mercaptoamino-anthraquinone. Instead of the o-aminothiophenols there may also be used their dithiosulfoxides obtained as preliminary products in the Herz chlorinesulfur reaction (cf. e. g. German patent specifications 360,690, and 367,346) with aromatic amines. I

For the dehydrocyclization with oxidizing agents nitrobenzene is particularly suitable, if desired, in the presence of alkaline agents such as potassium acetate or potassium carbonate. Preferably the reaction is carried out within a temperature range of about 150-215 C. (see also German'patent specification 366,272).

It is of special importance that it is not necessary'to use for the process according to the present invention the substituted free anthraquinone aldehydes obtainable only with difficulty, but that it is possible to start from the corresponding aldehyde-aniles which are readily obtain'able by reacting the nuclearly substituted 1-amind- Z-r'riethyl-anthr'aquinones with aniline in the presence of alkali and nitrobenzene at elevated temperature (see for example U. S. patent application Ser. No. 432,915, filed May 27, 1954).

The reaction of the aniles with the aromatic amino compounds is advantageously carried out in suitable solvents, such as glacial acetic acid or mixtures of glacial aceticwith other inert diluents such as chlorobenzene, or nitrobenzene and at elevated temperatures, for example within the range of about -200 0., preferably C.

The dyestuffs obtainable by the process of the present invention are distinguished by their especially valuable shades and fastness properties and great strength of color. The following examples are given for the purpose of illustrating the invention.

Example I A mixture consisting of 20 parts of 1-amino-4-benzoylamino-anthraquinone-Z-aldehyde-anile, parts of naphthalene, 30 parts of sulfur and 0.6 part of iodine is heated to 220 C. for 5 to 6 hours and then diluted with 150 parts of toluene. After cooling, the product is filtered off by suction and is freed in conventional manner from adhering naphthalene and by boiling out with sodium sulphide from excess sulfur. The new dyestuff, which is presumed to have the following formula II o NH.CO.CBH5

dissolves in concentrated sulfuric acid with an olive color. Upon addition of paraformaldehyde, the solution turns blue when cooled, and changes tobright violet when heated. Cotton is dyed from a cold, reddish violet vat in greyish blue shades fast to chlorine and having good fastness properties.

The 1 amino 4 benzoylamino-anthraquinone-2-aldehydeanile was obtained as follows:

50 parts of 1-amino-2-methyl-4-benzoylamino-anthraquinone, 25 parts of potassium carbonate and 10 parts of aniline are refluxed in 300 parts of nitrobenzene until a sample dissolves in pyridine with a clear blue color. The reaction mixture is filtered while hot. Upon cooling the 1-amino-4-benzoylamino-anthraquinone-Z-aldehyde anile crystallizes from the filtrate in dark blue prisms.

Example 2 15 parts of 1-amino-4-benzoylaminoanthraquinone-2- 5 aldehyde-anile are heated to the boil with 3.6 parts of 3.3-dihydroxy-benzidine in 300 parts of glacial acetic acid for 2 hours. The azomethine thus obtained crystallizes in blue needles; its constitution may be illustrated by the following formula EH HA H HC Patented Jan. 13, 1959 aeea'zee red-violet when heated. When using olive vat is obtained.

14 parts of the above azomethine are heated with 7 parts of potassium acetate and 250 parts of nitrobenzene to 210 C. until a sample shows under the microscope in stead of. the blue needles of the azomethine only small grey needles. The oxazole thus obtained having the hydrosulphite, an

4 green upon cooling and addition of paraformaldehyde, and bluish-violet on heating. The color of the vat is brown-yellow.

11.4 parts of the said azomethine are heated to the boil with 5.7 parts of potassium acetate in 150 parts of nitrobenzene until the dehydrogenation product is completely crystalline with small greyish violet needles. The oxazole is isolated in conventional manner and possesses is filtered ed by suction at about-90 C. washed with 1 presumably the following constitution a little nitrobenzene and freed from the solvent in conventional manner. The dyestufi obtained dissolves in concentrated sulfuric acid with a brownish yellow color.

Upon the addition of paraformaldehyde the color of the solution turns to a bluish green when cooled, to a bluish red when heated. The product dyes cotton from a ruby-colored vat in bluish-grey shades fast to chlorine and having very good general fastness properties.

In a similar manner a more greenish blue-grey may be obtained from 1-amino-4-p-methoXy-benzoylamino-anthraquinone-Z-aldehyde-anile. When using l-amino-- benzoyl-amino-anthraquinone-Z-aldehyde-anile a bluish violet dyestuff is obtained.

Example 3 A mixture of 7.43 parts of 1-amino-4-benzoylaminoanthraquinone-Z-aldehyde-anile, 4.89 parts of l-aminoathraquinone-2aldehyde-anile and 3.27 parts of: 3,3- dihydroXy-benzidine is heated to the boil in 360 parts of glacial acetic acid for 2 hours. The reddish blue crystals of the condensation product are, filtered off by suction and washed with water.

The solution of the azsomethine presumably possessing the following constitution CH H E B0 CO.CaHs

t W l o o-ii N 0 c (i It dissolves in concentrated sulfuric acid with a brownish yellow color which turns to a bluish green upon the addition of paraformaldehyde and cooling and to violet on heating. Cotton is dyed from a ruby-colored vat in bluish currant shades of very good fastness properties.

If in theexample 1-amino-4-benzoyl-amino-anthraquinone-Z-aldehydeaniIe is replaced by the corresponding- 5-benzoyl-amino derivative, a product is obtained dyeing-bluish red shades;

Example 4 lLs \l NH CuHsO is completely crystallized. in small. greyish blueneedles. The color of the solution of the isolated product is brownish yellow in concentrated sulfuric acid. Upon the addition of paraformaldehyde it turns to green when cooled is orange-red in concentrated sulfuric acid and. turns75 andto bluish red when heated. The dyestuff dyes cotton 5 6' from a bluish violet vat in beautiful grey shades of ZOYI-amino-anthfaquindne-z-aldehyde-anile in 150 Parts very good fastness properties. of nitrobenzene until formation of the small bluish green t Example 5 needles is terminated. V

If instead of 1-am1no-4-benzoyl-amlno-anthraquinonea m l mixture of y 2-aldehyde-anile, the derivative of S-benzoylamino is used,

thraquinone-2-aldehyde-anile, 1-amino-anthraquinone-2 a d tufi is obtained dyeing claret shades.

aldehyde-anile and 3,3'-dimercapto-benzidine :is coni densed and subsequently dehydrogenated in nitrobenzene, Example 7 a dyestufl is obtained which has presumably the follow' 14. 5 parts. of 6-chloro-l-amino-anthraquinone-Z-aldeingconstitution v e 10 hyde and 6.25 parts of o,o'-dimercapto benzidine are r m QQ c-s s-o I 0 I heated to the boil in 200 parts of nitro benzene until the 7 It dyes cotton from a violet vat m Currant Shades' 2o formation of the condensation product of the formula Example 6 is completed. The dyestuff'forrns blue red needles and is A mixture of 51 parts of 1 mercapto 2 amino anthra isolated in lrnown manner. It dyes cotton from a ruby quinone, and 8.9.parts of 1-amino-4-benzoylamino-anthracolPred Vat1 5 a blulsh bordeaux The fastngss prop quinone 2 a1dehyde ani1e. is condensed by heating in 250 ertles, especially the fastness to hght, are better than those parts of. glacial acetic acid yielding the violet cry t l which are obtained by using the chlorine free dyestuff of azomethine having the formula; (see German patent specification 366,272, Example 1).

(I) NH, N 0 Example 8 12 parts of 1-amino-4-(p-chloro-benzoylamino)-anthra- 1% quinone-Z-aldehyde-anile and 6 parts of 2-amino-3-hy 40 droxy-anthraquinone are heated in 180 parts of riitrobenzene and 25 parts of glacial acetic acid to 120 C. 1 until a worked up sample shows only the bluish violet I crystallizing condensation product of the formula 00.00116 7 O NH: O The azomethine dissolves in concentrated sulfuric acid I with a blue color which turns to greyish green upon cooling and addition of paraformaldehyde, upon heating to violet. Cotton is dyed in reddish blue shades which change 7 to green when treated with a soda solution, and to bluish green with chlorine water. I

If 7 parts of the azomethine in 100 parts of nitro- O benzene are heated to the boil, dehydration of the thiazole C sets in rapidly whlch crystallizes in bluish green small The i l acetic id i ow di tilled otf by heating needles and has the formula the melt to 200 C., then 7 parts of potassium acetate are 0 NH: N added and the melt is boiled for several hours until the H dehydrocyclisation is terminated.v The dyestuif thusobtained of the formula o H s o I IITH 00.60155 The thiazole dissolves in concentrated sulfuric acid l with a yellowish green color which turns to bluish green 0 Q upon coolmg and" addltlon of 'Paraformaldehyde and to crystallizes in blue needles and dyes cotton from a bluish viidlet 1 1 in T Product dyes cotton from violet vat in a reddish-blue shade which exhibits excellent dish violet vat 1n bluish green shades fast to chlorine fasmess properties and having an excellent fastness to light and very good The 1 amino 4 (p chloro benzoylamino) eneral fastness pr p Q anthraquinone 2 aldehyde anile was obtained as The same dyestuff may be obtained by a more simple f ll method by heating tov the boil 5.1 parts of 1-mer,capto-- 50 parts of. 1 amino-2-methyl-4 (p chloro-benzoyl- Z-amino-anthraquinone and 8.9 parts of l-ar nin o- 4-benamino)-anthraquinone, 25 parts of potassium carbonate and l'parts' of aniline arerefl'uxedin 300'parts of nitro cotton is dyed for about 45 minutes at 50 C. The dyebenzene until a sample dissolves in pyridine with a clear ing is oxidized in the usual manner on the air and there'- blue color. The reaction mixture is filtered. While hot. after rinsed and washed with Water containing 4 parts of Upon cooling the l-amino-4 (p chloro-benzoylarnino)- acetic acid per liter. The dyeing is then soaped, rinsed anthraquinone-2-aldehyde-anile crystallizes from the fil- 5 and dried in the usual manner. A bluish grey dyeing is trate in blue prisms. I obtained whichexhibits good fastnessproperties.

Example 9 I claim:

A mixture f 7 parts f l A pr'ocessfor the manufacture of vat dyestuffs amino-anthraquinone 2-aldehyde=anile', 2.92 parts of3,3 Whlch comPn'ses Teactmg member Sfflected from the dimercapto-benzidine (containing 85% of the pure com- 10 group Fonslstlng 0f q P l pound) and 100 parts of glacial acetic acid are heated to ("1111163 h Whlch are Substltuted the l the boil for about 2 hours. Thereafter the reaction qumone' nucleu? 93 at least Q mfimbel' selflwted' fmm product is filtered off and heated with 4.5 parts of potasgroup conslstmg of chlorme and y m r p sium acetate in 120 parts of nitrobenzene to the boil 15 at a tempelafilfe Within the range of all until the dyestufl? of the formula organic solvent selected from the group consisting of is formed in bluish grey needles. The dyestuff is then glacial acetic acid and mixtures of glacial acetic acid and inert organic diluents with amember selected from the group consisting of o,o'-dihydroXy-benzidine and filtered off and dissolves in concentrated sulfuric acid with a brownish-yellow color. It dyes cotton from a warm blue violet'vat in clear grey shades of good fa'st'riess o,o'-dimercapto-benzidine and subjecting the reaction properties. product obtained to a dehydrogenating cyclization With Example. 10 nitrobenzene at a temperature within the range of 150- 215 C. and recovering the reaction product formed.

02 part-ofthe dyestufi described in Example4 are 2. As novel dyestufi o NHz N 1 N NE: 0

II I l I 0 IIIH 1 111 00.09111 60.00115 dissolved at C. in 200 parts by volume of an aqueous 3. As novel dyestufi (10.05115 (30.00115 solution'containing'lA parts. by volume of sodium h'y- 4. As novel dyestufi droxide solution (38 B.), 0.8 part of sodium hydro- 5. Anovel dyestuif of the formula (6 NH: N N NE: H

snlfite and 4parts-ofssodium'sulfate. Fromthisdye bath wherein X"is a member selectedcfrom thegroup consisting of oxygen and sulfur and wherein at least on anthraquinone molecule is substituted at least once by a member selected from the group consisting of chlorine and acrylamino groups.

References Cited in the file of this patent UNITED STATES PATENTS 2,099,673 Beard Nov. 23, 1937 10 Cullinan et al Nov. 9, 1948 5 4th ed., 1st sup.), vol. 27, page 213 1938). 

5. A NOVEL DYESTUFF OF THE FORMULA 